Azo compounds and process for coloring therewith



Patented May 7, 1940 UNITED STATES PATENT OFFICE AZO COMPOUNDS AND PROCESS FOR COLORING THEREWI'I'H James G. McNally and Joseph B. Dickey, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing.

Application November 12, 1988,

Serial No. 240,1 1!

12 Claims.

wherein R represents the residue of an aromatic nucleus, R1 represents a member selected from the group consisting of hydrogen and an alkyl group, R2 and R: each represents a member selected from the group consisting of hydrogen, an alkyl group, an aralkyl group, an aryl group and a furyl group attached to the nitrogen atom through the carbon atom in" the 2-position by means of a saturated straight chain hydrocarbon radical containing not more than four carbon atoms and R4 and Rs each represents a member selected from the group consisting of hydrogen and an alkyl group constitute a valuable new class of dye compounds the members of which may be employed for the dyeing or'coloring of organic derivatives of cellulose, silk and wool as more fully set forth hereinafter.

The aromatic azo dye compounds of our invention can be prepared by coupling in an alkaline medium an aromatic diazonium compound with a heterocycllc coupling compound having the formula:

wherein R1, Ra, R3, R4, R5 have the meaning previously assigned-to them.

The nuclear non-sulfonated aromatic azo compounds of our invention constitute valuable dyes for the coloration of organic derivatives of cellulose such as cellulose acetate silk, for example. For the dyeing of organic derivatives of cellulose, compounds wherein R, represents the residue of an aryl nucleus of the benzene series have been found to be generally advantageous. The azo dye compounds of our invention may be generally employed, whether sulfonated or non-sulfonated, for the coloration of silk and wool. From the foregoing, it will be seen that by the use of a nuclear non-sulfonated dye, an organic derivative of cellulose, silk or wool may be dyed or mixtures of any two of these materials may be dyed. Similarly, it will be apparent that mixturesof the above materials may be dyed employing a mixture of sulfonated and nuclear nonsulfonated dyes. The dye compounds of our invention do not dye cotton or viscose and because of this can be used for cross dyeing mixtures of these materials with any or all of the above named materials. While the azo compounds of our invention may be employed to dye textile materials, forexample, made of or containing an organic derivative of cellulose, silk or wool, our invention is more particularly directed to the nuclear non-sulfonated compounds and their application for the dyeing or coloring of organic derivatives of cellulose, such as those mentioned hereinafter.

Organic derivatives of cellulose are characterized by an indifferent amnity for the usual cotton and wool dyes, especially the ordinary water soluble dyes. Because of this, it has been necessary to develop new dye compounds suitable for the dyeing .or coloration of materials such as textile materials made of or containing an organic derivative of cellulose. It is, accordingly, an object of our invention to provide a new class of azo dyes suitable for the dyeing or coloration or organic derivatives of cellulose.

Another object of our invention is to provide a process for the dyeing or coloration of organic derivatives of cellulose such as those hereinafter.

terials made of or containing an organic deriva- Example 1 12.3 grams of o-anisidine are added to 150 cc. of water to which has been added 25 cc. of 36% hydrochloric acid. The resulting solution 1 is cooled to a temperature approximating 0.5" C. by the addition of ice, for example, and the o-anisidine is diazotized while maintaining this temperature by adding, with stirring, 6.9 grams of sodium nitrite dissolved in water.

12.8 grams of are dissolved in 200cc. of water containing 30 grams of sodium carbonate. The resulting solution is cooled to a temperature approximating -10 C. by the addition of ice, for example, and

the diazonium compound prepared as described.

above is slowly added with stirring. Upon completion of the coupling reaction which takes place and which is carried out while maintaining a temperature of 0-10 0., the mixture is made acid to litmus by the addition of a mineral acid such as hydrochloric acid and the dye compound formed is recovered by filtration, washed with water and dried. The dye compound obtained colors cellulose acetate silk, wool and silk a greenish yellow shade.

Example 2 13.7 grams of p-phenetidine are diazotized in accordance with the method described in Exampie 1.

14.2 grams of are dissolved in 200 cc. of water containing 10 grams of sodium hydroxide and coupled in accordance with the method described in Example 1 with the diazonium compound, prepared as described above. The dye compound obtained colors cellulose acetate silk, wool and silk a greenish-yellow shade.

Example 3 15.1 grams of o-propoxyaniline are diazotized in accordance with the method described in Example l and the diazonium compound obtained is coupled with 14.2 grams of The coupling reaction and recovery of the dye compound may be carried out as described in Example l. The dye compound obtained colors cellulose acetate silk, wool and silk a greenish yellow shade.

Example 4 24.1 grams of 1-amino-2,6-di-p-methoxyethoxybenzene are diazotized in accordance with the method described in Example 1.

I 17 grams of E El 31H:

are dissolved in 200 cc. of water containing 10 grams of sodium hydroxide and coupled in accordance with the method described in Example 1 with the diazonium compound prepared as described above. The dye compound obtained colors cellulose acetate silk, wool and silk a greenish yellow shade.

Example 5 13.8 grams of o-nitroaniline are diazotized in known manner and the diazonium compound ob-.

tained is coupled with 15.6 grams of The coupling reaction and recovery of the dye I compound may be carried out as described in Example 1. The dye compound obtained colors cellulose acetate silk, wool and silk a greenish yellow shade.

Example 6 13.8 grams of p-nitroaniline are diazotized in known fashion and the diazonium compound obtained is coupled with 21.6 grams of I The dye compound obtained colors cellulose ace- The dye compound obtained colors cellulose acetate silk, wool and silk a greenish yellow shade.

Example 8 17.3 grams of 1-amino-2-nitro-4-chlorobenzene are diazotized in known fashion and coupled with 20.4 grams of The dye compound obtained colors cellulose acetate, wool and silk a greenish yellow shade.-

Example i) 27.2 grams of N01 cm I are added to 200 cc. of water to which has been added 40 cc. of 36% hydrochloric acid and the resulting mixture is diazotized at a temperature of 20 C. by the addition, with stirring, of 6.9 grams of sodium nitrite dissolved in water.

20.9 grams of i are dissolved ;in a .dilute aqueous sodium' car'- bonate solution and coupled with the diazonium compound prepared above .in accordance with the method described inExample 1. compound obtained'colors cellulose acetate silk a greenish-yellow shade.

Example 16 18.9 grams of '6-methoxy-2-aminobenzothia- 01 i v The dye Q are dissolved in a warm mixture oi'iiO grams of water, 25 grams of formic acid and grams of concentrated sulfuric acid, (specific gravity 1.84).

"The resulting solution is then cooled to a temperature of 5 C. and diazotized at this tem- ,perature by adding, with stirring, a water solution of 6.9 grams of sodium nitrite.

23.2 grams 0! are dissolved in 200 cc. of water containing. 10 grams of sodium hydroxide and coupled in accordance with the method described in Example 1 with the. diazonium compound prepared above. The dye compound obtained colors cellulose acetate silk, wool and silk 9. greenish-yellow shade.

Example 11 i 16 grams of 1-amino-8-naphthol-2,4-disulfonic acid are dissolved in cc. of water containing 11 grams of sodium carbonate. The resulting solution is cooled by the addition of ice and 7 resulting is then added dropwise to an iced solution of 50 grams of 36% hydrochloric acid in 50 grams of water whereby diazotization of the '1- amino-8-naphthol-2,4-disulfonic acid is efiected. 9.3 grams of are dissolved in a dilute aqueous sodium hydroxide, the resulting solution is cooled to a temperature approximating 0-10 0. and following this the diazonium compound prepared above is slowly added with stirring. Upon completion of the coupling reaction which takes place, the mixture is made acid to litmus by the addition of hydrochloric acid and the dye compound is salted out .by the addition of sodium chloride, recovered by filtration, washed and dried. The dye compound obtained colors wool and silk a yellow shade.

5.4 grams of -2-amino-5-nitrobenzenesulfonic acid or 11.95 grams of 1-amino-2-naphthol-4- sulfonic acid, for example, can be substituted for the l-amino-8-naphthol-2,4-disulfonic acid of grams of sodium nitrite are added. The solution the example and upon diazotization in known-v fashion can be coupled with the coupling component just mentioned or with any of the other coupling components mentioned herein to ob-' tain dye compounds within the scope of our invention which are ofvalue for the'dyeing of wool and silk. v

The following tabulation further illustrates the compounds employed in the process of my invention together with the color they produce on cellulose acetate silk. The compounds indicated belowmay be prepared by diazotizing the amine. listed under the heading Amine" and coupling the diazonium compounds obtained with the compounds speciiied in the column entitled Coupling component. The diazotization and coupling'reactions mayyfor example, be carried out following the general procedure described in Examples for the most part, relatively insoluble in water.

1 to 11 inclusive.

Color on cellulose Amine Coupling component mm m Aniline (l) 0:0-2'3 Greenish-yollow.

Do (2) =ON-CB; Do- 41H: H

cm O=C-NH 2 Do a o=c .No,mon Do.

m H: s.

Bic-CH:

D0 (4) O=C-N-CH:'H CH, Do.

p-Anisidino D0. o-Phenetidin Do.

I o-Phenoxyanilino Do.

J0 o-To uidino Do. o-(Cl, Br. l)-anlline Do.

o-B-h droxyothorinniline Do. l-amino-zi-dimet oxybenzene D0. l-amino-z-methoxy-fi-ethoxy benzenohn Do. l-amino-2-nephtholmethyl-ether Do. o-Nitroanilin D0.

l-amino-z-nltro-i-chlorobenzene Do. Dianisidine Do. z-amlno-o-methoxybenzothiaml Do. p-Aminophenol Do. o-Aminobenmic acid ethyl Do. o-Amino do Do. p-Aminodimcthylaniline l-4 above Red.

v Preparation of 0==CNH HI T e O=G KH 23 grams of sodium are dissolved in 400 cc. of absolute ethanol and 160 grams of ethyl malonate are added following which 50 grams of ethylene diamine are also added. The reaction mixture resulting is refluxed with stirring for six hours. Upon completion of the refluxing, most of the is made slightly acid to litmus by the addition of aceti or hydrochloric acid. 0n standing, the

desired )compound separates out and may be recovered by filtration, washed with water and dried.

5 The' azo dye compounds of our invention are,

.ethanol is distilled off and the mixture resulting may be advantageously employed for the direct dyeing of textile materials by grinding the dye to a fine powder, intimately mixing it with a suitable dispersing or solubilizing agent, and adding the resulting mixture to water or adilute solution of soap in water to form an aqueous dyebath. Following this known preparation of the dyebath, the textile materials to be dyed may be added to the dyeb'ath and the dyeing operation conducted in known fashion. The dye compounds of our invention which are water soluble do not, of course, require the use of a dispersing or solubilizing agent but may be applied to silk, wool and (depending upon the nature and position of the water-solubilizing group) organic derivatives of cellulose textile materials from an aqueous solution of the dye which may contain salt. For a more complete description as to how the. azo dye compounds of our invention may be employed in dyeing or coloring operations, reference may be had to our U. S. Letters Patent No. 2,115,030, issued April 26, 1938. For a more detailed description as to how the water soluble azo dyes of our invention may. be employed for the coloration of textile materials made of-or containing organic derivatives of cellulose, silk and wool or mixtures of these, reference may be had to our U. S. Letters Patent No. 2,107,898, issued February 8, 1938.

We claim:

1. Azo dye. compounds having the general formula: 3

- =C--NRg o= --lI--R wherein R represents the residue of an aromatic nucleus, Rrrepresents a member selected from thegroup consisting of hydrogen and an alkyl group, R: and Rs each represents a "member selected from the group consisting of hydrogen, an alkyl ,group, an aralkyl group, an aryl group and a iuryl group attached to the nitrogen atom through the carbon atom in the 2-position by means-of a saturated straight chain hydrocarbon radical containing not more than four carbon atoms and R4 and Rs each represents a member selected irom the group consisting of hydrogen and an alhl group.

2. Azodye compounds having the general wherein R represents the residue of an aryl nucleus of the benzene series, R1 represents a member selectedvtrom the group consisting of hydrogen and an alkyl group, R: and R3 each represents a member selected from the group wherein R represents the residue 0! an aryl nucleus of the benzene series. R1 represents a member selected from the group consisting of hydrogen and an represents a member selected from the group consisting of hydrogen, an alkyl group, an aralkyl group. an aryl group and a iuryl groupattached to the nitrogen atom through the carbon atom in the 2-position by means of asaturated straight chain hydrocarbon radical containing not more '"thamtom carbon atoms and R and R eaoh general formula:

E JJRRaandRaeach' replaced with an alkyl group.

represents a memberselected from the group consisting of hydrogen and an alkyl group.

4. Nuclear non-sulion'ated monoazo dye compounds having the general formula:

s 4 0=CNH wherein R represents the residue of an aryl nucleus of the benzene series, wherein each of the hydrogen atoms, in the l, .4 and 6 positions of the heterocyclic nucleus maybe replaced with an alkyl group and wherein one of the-hydrogen atoms in each of the 2 and 3 positions may be replaced with an alkyl group. i I

'5. Monoazo dye compounds having the general formula:

' O=CNH R N-NI H r (IJH: .0: .'m wherein R represents the residue of an aryl nucleus of the benzene series. v

6. The process of coloring material made of or containing an organic derivative of cellulose which comprises applying thereto a nuclear nonsulronated azo dye compound having the general wherein R represents the residue 01' an aromatic nucleus, R1 represents a member selected from the group consisting of hydrogen and an allwl group, R2 and R3 each represents a member selected from the group consisting of hydrogen, an alkyl group,an aralkyl group, an aryl group and a furyl group attached to the nitrogen atom through the carbon atom in the 2-position by means of a'saturated straight chain hydrocarbon radical containing not more than four carbon atoms and R4 and R5 each represents a member selected from the group consisting of hydrogen and an alkyl group.

7. The process of coloring material made of or containing an organic derivative of cellulose which comprises applying thereto a nuclear nonsulfonated monoazo dye compound having the wherein R represents the residue of an aryl nucleus of the benzene series,wherein each of fire hydrogen atoms in the 1, 4 and 6 positions of e heterocyclic nucleus may be replaced with an allnvl group and wherein one of the hydrogen atoms in eacliv of the 2 and 3 positions may be 8. The process of coloring a cellulose acetate which comprises applying thereto a nuclear nonsulfonated azo dye compound having tlfi general formula:

wherein R represents the residue of an aromatic nucleus, R1 represents a member selected from the group consisting of hydrogen and an alkyl group, R2 and each represents a member selected from the group consisting of hydrogen, an alkyl group, an aralkyl group, an aryl group and a furyl group attached to the nitrogen atom through the carbon atom in the 2-position bymeans of a saturated straight chain hydrocarbon radical containing not more than four carbon I atoms and R4 and R5 each represents a member selected from the group consisting of hydrogen and an alkyl group.

9. Material made of or containing an organic derivative of cellulose colored with a nuclear nonsulfonated monoazo dye compound having the general formula:

wherein R represents the residue of an aryl nucleus of the benzene series, R1 represents a member selected from the group consisting of hydrogen and an alkyl group, R2 and R3 each represents a member selected from the group consisting of hydrogen, an alkyl group, an aralkyl group, an

aryl group and a furyl group attached to the nitrogen atom through the carbon atom in the 2-position by means of a saturated straight chain hydrocarbon radical containing not more'than tour carbon atoms and R4 and R5 each represents 5 a member selected from the group consisting of hydrogen and an alkyl group.

10. A cellulose acetate colored with a nuclear nonsuli'onated monoazo dye the general formula:

compound having rated straight chain hydrocarbon radical containing not more than four carbon atoms and R4 and Rs each represents a member selected from the group consisting of hydrogen and an alkyl group.,

11. A cellulose acetate colored with a nuclear non-sulfonated monoazo dye .compound having the general formula:

wherein R represents the residue of anaryl nucleus of the benzene series; wherein each of the hydrogen atoms in the 1,.4 and 6 positions of the heterocyclic nucleus may be replaced with an alkyl group and wherein one of the hydrogen atoms in each of the 2 and 3 positions may be replaced with an alkyl group. Y

12. A cellulose acetate colored with a nuclear non-sulfonated monoazo dye compound having the general formula:

wherein R represents the residue of an aryl nucleus of the benzene series.

' JAMES G. McNALLY.

JOSEPH B. DICKEY. 

